EP1695146B1 - COATING MATERIALS CONTAINING alpha-(1 -HYDROXYALKYL)ACRYLATES - Google Patents

Abstract

Coating compositions comprising alpha-(1'-hydroxyalkyl)acrylates, processes for preparing them, and their use.

Description

The present invention relates to coating compositions containing α- (1'-hydroxyalkyl) acrylates, processes for their preparation and their use.

α- (1'-hydroxyalkyl) acrylates can be prepared via the so-called Baylis-Hillman reaction, in which acrylates and aldehydes are reacted with one another.

US 5,380,901 describes the reaction of acrylates with para-formaldehyde to form ether-bridged diacrylates as well as the reaction of diacrylates with formaldehyde to di (.alpha .- (1'-hydroxyalkyl)) acrylates and the potential use of such monomers in, for example, coatings. As curing, only bulk polymerization is described.

US-B1 6,482,568 describes by excimer laser radiation-curable resin compositions for photoresists, which are composed of special norbornene derivatives as monomers and may optionally contain copolymerized as further monomers α-hydroxymethyl acrylates.

The specific resin compositions described therein are also made by bulk polymerization only and the polymerized resins are designed to cure only at certain wavelengths in lithography and are not widely applicable.

The object of the present invention was to provide improved monomers for dual-cure coating compositions.

worin
R² und R³ unabhängig voneinander C₁ - C₁₈-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂ - C₁₈-Alkyl, C₂ - C₁₈-Alkenyl, C₆ - C₁₂-Aryl, C₅ - C₁₂-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können,
R² und/oder R³ zusätzlich Wasserstoff, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C₁ - C₁₈-Alkoxy oder -COOR⁴,
R² kann zusätzlich zusammen mit R¹ einen Ring bilden, in diesem Fall kann R² eine Carbonylgruppe bedeuten, so daß die Gruppe COOR¹ und R² gemeinsam eine Säureanhydridgruppe -(CO)-O-(CO)- bilden,
R⁴ C₁ - C₁₈-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂ - C₁₈-Alkyl, C₂ - C₁₈-Alkenyl, C₆ - C₁₂-Aryl, C₅ - C₁₂-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können,
R⁵ und R⁶ unabhängig voneinander Wasserstoff, C₁ - C₁₈-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂ - C₁₈-Alkyl, C₂ - C₁₈-Alkenyl, C₆ - C₁₂-Aryl, C₅ - C₁₂-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können, oder können gemeinsam einen Ring bilden,
n eine positive ganze Zahl von 3 bis 10,
R⁷ einen n-wertigen organischen Rest mit 1 bis 50 Kohlenstoffatomen, der unsubstituiert oder mit Halogen, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, Carboxy, Carboxy-C₁-C₈-Alkyl, C₁-C₂₀-Acyl, C₁-C₈-Alkoxy, C₆-C₁₂-Aryl, Hydroxy oder hydroxysubstituiertem C₁-C₈-Alkyl substituiert sein und/oder eine oder mehrere -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- oder -(CO)O-Gruppen aufweisen kann.The object has been achieved by compounds of the formula (V),

wherein
R ² and R ^{3 are} independently C ₁ - C ₁₈ alkyl, optionally by one or more Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C ₂ - C ₁₈ alkyl, C ₂ - C ₁₈ alkenyl, C ₆ - C ₁₂ aryl, C ₅ - C ₁₂ cycloalkyl or a a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, where the radicals mentioned may each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
R ² and / or R ³ additionally hydrogen, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkoxy or -COOR ⁴ ,
R ² may additionally form a ring together with R ¹ , in which case R ^{2 may represent} a carbonyl group, so that the group COOR ¹ and R ² together form an acid anhydride group - (CO) -O- (CO) -,
R ^{4 is} C ₁ -C ₁₈ -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, C ₆ interrupted C ₁₂ -aryl, C ₅ -C ₁₂ -cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle, where the radicals mentioned in each case by aryl, alkyl, aryloxy, alkoxy, heteroatoms and / or Heterocycles can be substituted,
R ⁵ and R ^{6 are} independently hydrogen, C ₁ -C ₁₈ -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ -alkyl, C ₂ - C ₁₈ alkenyl, C ₆ -C ₁₂ -aryl, C ₅ -C ₁₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein said radicals are each represented by aryl, alkyl, aryloxy , Alkyloxy, heteroatoms and / or heterocycles, or may together form a ring,
n is a positive integer from 3 to 10,
R ^{7 is} an n-valent organic radical having 1 to 50 carbon atoms which is unsubstituted or halogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, carboxy, carboxy-C ₁ -C ₈ alkyl, C ₁ -C ₂₀ acyl, C ₁ -C ₈ alkoxy, C ₆ -C ₁₂ aryl, hydroxy or hydroxy-substituted C ₁ -C ₈ alkyl and / or one or more - (CO) -, -O (CO ) O, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O groups.

In the context of this document, the term "dual cure" or "multi-cure" refers to a hardening process which takes place via two or more than two mechanisms, for example selected from radiation, moisture, chemical, oxidative and / or thermal curing, preferably selected from radiation, moisture, chemical and / or thermal curing, particularly preferably selected from radiation, chemical and / or thermal curing and most preferably radiation and chemical curing.

Radiation hardening in the sense of this document is defined as the polymerization of polymerizable compounds as a result of electromagnetic and / or corpuscular radiation, preferably UV light in the wavelength range of λ = 200 to 700 nm and / or electron radiation in the range of 150 to 300 keV and more preferably with a radiation dose of at least 80, preferably 80 to 3000 mJ / cm ² .

Chemical curing in the context of this document is defined as the polymerization of polymerizable compounds as a result of a reaction of hydroxyl groups (-OH) with hydroxyl (-OH) reactive groups, for example isocyanates, capped isocyanates, epoxides, carbonates or aminoplasts, preferably isocyanates, epoxides or Aminoplasts, more preferably isocyanates or epoxides, and most preferably isocyanates.

Suitable α- (1'-hydroxyalkyl) acrylates (A) may be one or more, for example 1 to 10, preferably 1 to 6, particularly preferably 1 to 4, very particularly preferably 2 to 4 and in particular 3 to 4 α- (1 ' -Hydroxyalkyl) acrylate groups,

The number average molecular weight M _{n of} these compounds (A), determined by gel permeation chromatography with tetrahydrofuran as eluent and polystyrene as standard, can be, for example, up to 10,000, preferably up to 5000, more preferably between 100 and 2000 and in particular between 100 and 1000 g / mol ,

Examples of such α- (1'-hydroxyalkyl) acrylates (A) are compounds obtainable by reacting a mono- or polyfunctional acrylate with a monofunctional or polyfunctional carbonyl compound.

Examples of carbonyl compounds are aldehydes or ketones, preferably aldehydes.

This may be the reaction of a monofunctional acrylate (I) with a monofunctional carbonyl compound (II).

Furthermore, it may be the reaction of a polyfunctional acrylate (IV) with a monofunctional carbonyl compound (II).

Furthermore, it may be the reaction of a polyfunctional acrylate (I) with a polyfunctional carbonyl compound (VI).

Mean in it
R ¹ , R ² and R ^{3 are} independently C ₁ -C ₁₈ -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ -alkyl, C ₂ interrupted C ₁₈ -alkenyl, C ₆ -C ₁₂ -aryl, C ₅ -C ₁₂ -cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle, where the radicals mentioned are in each case represented by aryl, alkyl, Aryloxy, alkyloxy, heteroatoms and / or heterocycles may be substituted,
R ² and / or R ³ additionally hydrogen, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkoxy or -COOR ⁴ , R ² may additionally form a ring together with R ¹ , in which case R ^{2 may represent} a carbonyl group, so that the group COOR ¹ and R ² together form an acid anhydride group - (CO) -O- (CO) -,
R ⁴ has the same meaning as listed for R ¹ , but may be different from this,
R ⁵ and R ^{6 are} independently hydrogen, C ₁ -C ₁₈ -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ -alkyl, C ₂ - C ₁₈ alkenyl, C ₆ -C ₁₂ -aryl, C ₅ -C ₁₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein said radicals are each represented by aryl, alkyl, aryloxy , Alkyloxy, heteroatoms and / or heterocycles, or may together form a ring,
n is a positive integer from 2 to 10,
R ^{7 is} an n-valent organic radical having 1 to 50 carbon atoms which is unsubstituted or halogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, carboxy, carboxy-C ₁ -C ₈ alkyl, C ₁ -C ₂₀ acyl, C ₁ -C ₈ alkoxy, C ₆ -C ₁₂ aryl, hydroxy or hydroxy-substituted C ₁ -C ₈ alkyl and / or one or more - (CO) -, -O (CO ) O-, - (NH) (CO) O-, -O (CO) (NH) -. May have -O (CO) - or- (CO) O- groups and
R ^{8 represents} unsubstituted or with halogen, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, carboxy, carboxy-C ₁ -C ₈ -alkyl, C ₁ -C ₂₀ -acyl, C ₁ -C ₈ - Alkoxy, C ₆ -C ₁₂ -aryl, hydroxyl or hydroxy-substituted C ₁ -C ₈ -alkyl-substituted C ₆ -C ₁₂ -arylene, C ₃ -C ₁₂ -cycloalkylene, C ₁ -C ₂₀ -alkylene or by one or more Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -O (CO) O-, - (NH) (CO) O-, -O ( CO) (NH) -, -O (CO) - or - (CO) O groups interrupted C ₂ -C ₂₀ alkylene or a single bond.

Mean in it
optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1 -Phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl , 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, Diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl,
2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6- Dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6- Methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl,
optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkoxy, for example methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy, tert -Butyloxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12- Ethoxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 8- Methoxy-1,5-dioxooctyl, 12-methoxy-1,5,9-trioxooctyl, 16-methoxy-1,5,9,13-tetraoxohexadecyl, 8-ethoxy-1,5-dioxooctyl, 12-ethoxy-1, 5,9-trioxooctyl, 16-ethoxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxo-pentadecyl, 10-methoxy-1,6- dioxodecyl, 15-methoxy-1,6,11-trioxo-pentadecyl, 10-ethoxy-1,6-dioxodecyl or 15-ethoxy-1,6,11-trioxo-pentadecyl,
optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ - C ₁₈ -alkyl, for example, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa- octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa pentadecyl, 9-hydroxy-5-oxa-rionyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy-3, 6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5- oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxo-octyl, 11-ethoxy-3,6,9-trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy 5,10-oxa-tetradecyl.

The number of oxygen and / or sulfur atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.

Furthermore, at least one carbon atom, preferably at least two, is usually present between two heteroatoms.

Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso- propylimino, n-butylimino or tert- butylimino.

Furthermore means
C ₂ -C ₁₈ -alkenyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, Undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
C ₆ -C ₁₂ aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chlomaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl , 2,6-dimethoxyphenyl, 2,6-dichlorophenyl,
4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
optionally C ₅ -C ₁₂ -cycloalkyl which is substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, Butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, Methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and
C ₁ to C ₄ alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

The number of substituents in the indicated radicals is not limited. In general, it is up to 3 substituents, preferably up to 2 and particularly preferably up to one with radicals having one to three carbon atoms. In the case of radicals having four to six carbon atoms, it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one. For radicals with more than seven carbon atoms, it is usually up to 6 substituents, preferably up to 4 and more preferably up to two.

R ¹ is preferably C ₁ -C ₁₈ -alkyl or C ₅ -C ₁₂ -cycloalkyl which is substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec- Butyl, tert -butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl , Methylcyclohexyl, dimethylcyclohexyl, norbornyl or norbornenyl, more preferably R ^{1 is} methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2-hydroxyethyl , 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl or 6-hydroxyhexyl, very particularly preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or 2-ethylhexyl and in particular methyl, ethyl, n-butyl or 2-ethylhexyl.

R ² is preferably hydrogen, C ₁ -C ₁₈ -alkyl substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles or a carbonyl group which is connected to R ¹ , so that the group COOR ¹ and R ² together form a Acid anhydride group - (CO) -O- (CO) - form, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably hydrogen or methyl and especially hydrogen.

R ³ is preferably hydrogen, substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkyl, particularly preferably hydrogen, or C ₁ -C ₄ -alkyl, which for the purposes of this specification means methyl, ethyl , Propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, very particularly preferably hydrogen or methyl and especially hydrogen.

R ⁴ is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, more preferably methyl or ethyl.

R ⁵ and R ⁶ are each independently preferably hydrogen, C ₁ -C ₁₈ -alkyl substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, C ₂ -C ₁₈ -alkenyl, C ₆ -C ₁₂ -aryl or C ₅ - C ₁₂ cycloalkyl, more preferably hydrogen, substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ₁ - C ₁₈ alkyl or C ₆ - C ₁₂ aryl, very particularly preferably hydrogen, methyl, Ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, benzyl, tolyl, o-, m- or p-xylyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl or 2-, 3- or 4-nitrophenyl and especially hydrogen, methyl, ethyl, propyl, isopropyl or phenyl.

Preferably, at least one of the two radicals R ⁵ and R ^{6 is} hydrogen.

R ⁷ is preferably an organic radical derived from an n-valent alcohol by removal of n-hydroxy groups, for example derived from di- to trihydric alcohols, more preferably derived from di- to hexahydric alcohols, most preferably derived from di- to tetrahydric alcohols and especially derived from dihydric to trihydric alcohols.
R ⁸ is preferably unsubstituted or substituted by halogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, carboxy, carboxy-C ₁ -C ₈ alkyl, C ₁ -C ₂₀ acyl, C ₁ -C _8- alkoxy, C ₆ -C ₁₂ -aryl, hydroxyl or hydroxy-substituted C ₁ -C ₈ -alkyl-substituted C ₆ -C ₁₂ -arylene, C ₃ -C ₁₂ -cycloalkylene or C ₁ -C ₂₀ -alkylene or by a or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -O (CO) O-, - (NH) (CO) O-, - O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C ₂ -C ₂₀ -alkylene or a single bond, particularly preferably unsubstituted or with halogen, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, carboxy, carboxy-C ₁ -C ₈ -alkyl, C ₁ -C ₂₀ -acyl, C ₁ -C ₈ -alkoxy, C ₆ -C ₁₂ -aryl, hydroxyl or hydroxy-substituted C ₁ - C ₈ alkyl substituted C ₁ -C ₂₀ alkylene or a single bond and most preferably unsubstituted or with halogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ - Alkenyl, carboxy, carboxy-C ₁ -C ₈ -alkyl, C ₁ -C ₂₀ -acyl, C ₁ -C ₈ -alkoxy, C ₆ -C ₁₂ -aryl, hydroxyl or hydroxy-substituted C ₁ -C ₈ -alkyl substituted C C ₁ -C ₂₀ -alkylene.

Examples of compounds (I) are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 5 Hydroxy-3-oxa-pentyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, dihydrodicyclopentadienyl acrylate, norbornyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cyclododecyl acrylate, phenyl acrylate, crotonic acid methyl ester, crotonic acid ethyl ester, maleic anhydride, dimethyl maleate, diethyl maleate, maleic di-n butyl ester, dimethyl fumarate or diethyl fumarate.

Preferred compounds (I) are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate.

Particularly preferred compounds (I) are methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.

Examples of compounds (II) are formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, heptanal, nonanal, cyclopentylaldehyde; Cyclohexylaldehyde, benzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methoxybenzaldehyde, 4-methylbenzaldehyde, phenylacetaldehyde, salicylaldehyde, chloralhydrate, 4-dimethylaminobenzaldehyde, furfural, 2-nitrobenzaldehyde, vaniline, anisaldehyde, cinnamaldehyde, Pyridinecarbaldehyde, hydroxypivalaldehyde, dimethylolpropionaldehyde, dimethylolbutyraldehyde, trimethylolacetaldehyde, acetone, ethyl methyl ketone, diethyl ketone, methyl vinyl ketone, isobutyl methyl ketone, acetophenone, propiophenone, benzophenone, cyclopentanone, cyclohexanone or cyclododecanone.
Preferred compounds (II) are the aldehydes listed, particularly preferred are formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, hydroxypivalaldehyde, dimethylolpropionaldehyde, dimethylolbutyraldehyde and trimethylolacetaldehyde, most preferably formaldehyde , Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde and dimethylolbutyraldehyde, and especially formaldehyde.

It is advantageous for the production of non-ether-bridged Baylis-Hillman products to use aldehydes in free form, ie the formation of formals of these aldehydes of the formula (R ⁵ -CHO) _w , where w is a positive integer, by using suitable aldehydes or Repress choice of suitable solvents. While in US 5,380,901 due to the use of para-formaldehyde or para-formaldehyde / DMSO, in which the formation of formals is not suppressed, consistently ether-bridged systems are obtained, it is advantageous to use aldehydes with a high proportion of lower formal, for example w ≤ 20, preferably w ≦ 10, and more preferably w ≦ 5.

The proportion of these lower formals should, based on the total amount of aldehyde, be for example at least 50%, preferably at least 60%, particularly preferably at least 70% and very particularly preferably at least 80%.

This is achieved in the case of formaldehyde, for example, by using formaldehyde in the form of aqueous solutions, for example not more than 49% pure and preferably up to 37% pure.

These measures make it possible to reduce the proportion of ether-bridged Baylis-Hillman products. This proportion is determined as a molar proportion of the aldehyde equivalents in ether linkages (-CHR ⁵ -O-CHR ⁵ -) on the sum of the Baylis-Hillman products, ie ether linkages and terminal -CHR ⁵ OH groups.

The ether linkages thus correspond to 2 molar equivalents of aldehyde R ⁵ -CHO, whereas the terminal -CHR ⁵ OH groups correspond to one molar equivalent of aldehyde.

The determination of the proportions of the groups can be carried out, for example, by NMR spectroscopy. In the case of formaldehyde, the CH ₂ -O-CH ₂ group appears in ¹ H NMR spectra in CDCl ₃ as a singlet or a singlet split by allyl coupling at ca. δ = 4.22 ppm (cf. US 5,380,901 ) and the CH ₂ OH group at about 4.30 ppm or in ¹³ C NMR spectra in CDCl _3, the CH ₂ -O-CH ₂ group at about δ = 68.7 ppm and the CH ₂ OH Group at about 62.0 ppm.

As a result of the abovementioned measures according to the invention for the use of aldehydes with a low proportion of formals, the proportion of ether compounds can generally be 50% or less, preferably 40% or less, more preferably not more than 33%, very particularly preferably not more than 25% and in particular to not more than 15%.

On the other hand, the proportion of ether bridging in the US 5,380,901 Column 5 shown silicone diacrylate with n = 2 and 95% x = -CH ₂ OH ( US 5,380,901 , Column 5, lines 57-59) about 69%. However, a high proportion of terminal OH groups is advantageous in the dual-cure cure for reaction with OH-reactive groups.

Examples of compounds (IV) are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate , Neopentyl glycol diacrylate, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol diacrylate, 1,2-, 1,3- or 1,4-cyclohexanediol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane penta- or hexaacrylate, pentaerythritol triacrylate. or tetraacrylate, glycerol di- or triacrylate, and di- and polyacrylates of sugar alcohols, such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt , or polyester polyols, polyetherols, poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 1178, polyethylene glycol having a molecular weight between 106 and 898, and urethane acrylates or polycarbonate acrylates.

worin
R⁹ und R¹⁰ unabhängig voneinander Wasserstoff oder C₁- C₁₈-Alkyl,
k, l, m, q unabhängig voneinander je für eine ganze Zahl von 1 bis 10, bevorzugt 1 bis 5 und besonders bevorzugt 1 bis 3 steht und
jedes X_i für i = 1 bis k, 1 bis l, 1 bis m und 1 bis q unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CHVin-O-, -CHVin-CH₂-O-, -CH₂-CHPh-O- und -CHPh-CH₂-O-, bevorzugt aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O- und -CH(CH₃)-CH₂-O-, und besonders bevorzugt -CH₂-CH₂-O-,
worin Ph für Phenyl und Vin für Vinyl steht.Further examples are acrylates of compounds of the formulas (IVa) to (IVc)

wherein
R ⁹ and R ¹⁰ independently of one another are hydrogen or C ₁ -C ₁₈ -alkyl,
k, l, m, q independently of one another are each an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3, and
each X _i for i = 1 to k, 1 to 1, 1 to m and 1 to q may independently be selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O -, -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CHVin-O -, -CHVin-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,
where Ph is phenyl and Vin is vinyl.

These are preferably acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

Preferred compounds (IV) are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyesterpolyol acrylates, polyetherol acrylates and triacrylate of one to twenty times ethoxylated trimethylolpropane.

Particularly preferred compounds are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane.

• Oxalsäure, Maleinsäure, Fumarsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure, Dodekandisäure, o-Phthalsäure, Isophthalsäure, Terephthalsäure, Trimellithsäure, Azelainsäure, 1,4-Cyclohexandicarbonsäure oder Tetrahydrophthalsäure, Korksäure, Azelainsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäureanhydrid, dimere Fettsäuren, deren Isomere und Hydrierungsprodukte sowie veresterbare Derivate, wie Anhydride oder Dialkylester, beispielsweise C₁-C₄-Alkylester, bevorzugt Methyl-, Ethyl- oder n-Butylester, der genannten Säuren eingesetzt werden. Bevorzugt sind Dicarbonsäuren der allgemeinen Formel HOOC-(CH₂)_y-COOH, wobei y eine Zahl von 1 bis 20, bevorzugt eine gerade Zahl von 2 bis 20 ist, besonders bevorzugt Bernsteinsäure, Adipinsäure, Sebacinsäure und Dodecandicarbonsäure.
  Als mehrwertige Alkohole kommen zur Herstellung der Polyesterole in Betracht 1,2-Propandiöl, Ethylenglykol, 2,2-Dimethyl-1,2-Ethandiol, 1,3-Propandiol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 3-Methylpentan-1,5-diol, 2-Ethylhexan-1,3-diol, 2,4-Diethyloctan-1,3-diol, 1,6-Hexandiol, Poly-THF mit einer Molmasse zwischen 162 und 2000, Poly-1,3-propandiol mit einer Molmasse zwischen 134 und 1178, Poly-1,2-propandiol mit einer Molmasse zwischen 134 und 898, Polyethylenglykol mit einer Molmasse zwischen 106 und 458, Neopentylglykol, Hydroxypivalinsäureneopentylglykolester, 2-Ethyl-1,3-Propandiol, 2-Methyl-1,3-Propandiol, 2,2-Bis(4-hydroxycyclohexyl)propan, 1,1-, 1,2-, 1,3- und 1,4-Cyclohexandimethanol, 1,2-, 1,3- oder 1,4-Cyclohexandiol, Trimethylolbutan, Trimethylolpropan, Trimethylolethan, Neopentylglykol, Pentaerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Sorbit, Mannit, Diglycerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit oder Isomalt.

Polyester polyols are, for example Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 19, pp. 62 to 65 known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols become. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include:

• Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, suberic, azelaic, phthalic, tetrahydrophthalic, hexahydrophthalic, tetrachlorophthalic, endomethylenetetrahydrophthalic, Glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products and esterifiable derivatives such as anhydrides or dialkyl esters, for example C ₁ -C ₄ alkyl esters, preferably methyl, ethyl or n-butyl esters, of the acids mentioned are used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH ₂ ) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  Suitable polyhydric alcohols for the preparation of the polyesterols are 1,2-propane oil, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol of molecular weight between 134 and 1178, poly-1,2-propanediol of molecular weight between 134 and 898, polyethylene glycol of molecular weight between 106 and 458, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1 , 2-, 1,3- or 1,4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite) , Xylitol, dulcitol (galactitol), maltitol or I. somalt.

Alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. Preferred are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further preferred is neopentyl glycol.

Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Preferred lactones are those which are derived from compounds of the general formula HO- (CH ₂ ) _z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit may also be substituted by a C ₁ - to C ₄ -alkyl radical. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Examples of compounds (VI) are glyoxal, succinaldehyde, glutaraldehyde, capronaldehyde, phthalaldehyde or terephthalaldehyde, preferably glyoxal.

Another object of the present invention are compounds of formula (V) in which n is at least 3 and preferably 3 or 4. Very particular preference is given to those compounds in which the radical R ^{7 is} derived from optionally alkoxylated trimethylolpropane or pentaerythritol. Due to the simultaneous presence of acrylate and hydroxyl groups, these compounds have a particularly good suitability for dual-cure curing. It is surprising in knowledge of the teaching of US 5,380,901 in that, despite the higher density of the hydroxy groups and their spatial proximity, no increased proportion of ether linkages was found as defined above.

The implementation of the Baylis-Hillman reaction is known per se to the person skilled in the art and is described, for example, in US Pat HMR Hoffmann, J. Rabe, Angew. Chem., Int. Ed. Engl., 22, 1983, 795-796 and 796-797 . A. Foucaud, E. le Rouille, Synthesis, 1990, 787-789 . Y. Fort, M.-C. Berthe, P. Caubere, Synthetic Communications, 1992, 22 (9), 1265-1275 or D. Basaviah, PD Rao and RS Hyma. Tetrahedron, 1996, 52 (24), 8001-8062 ,

The reaction can be carried out at a temperature between 0 ° C and 100 ° C, preferably 20 to 80 ° C and particularly preferably 25 ° C to 60 ° C.

To react ketones, it may be necessary to apply high pressure as described in D. Basaviah et al, supra, p. 8004.

As the catalyst for the reaction is usually a tertiary amine or phosphine, used, for example, trimethylamine, triethylamine, tri-n-butylamine, ethyl-di- iso -propylamine, methyl-di- iso -propylamine, N-methylmorpholine, N-methylpiperidine, Triethanolamine, N, N-dimethylethanolamine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU ), Pyrroline, quinuclidine, quinidine, Trimethylphosphine, triethylphosphine, tri-n-butylphosphine, dimethylphenylphosphine, the tertiary amines or phosphines listed in D. Basaviah et al, loc. Cit., Pp. 8053-8054 or preferably 1,4-diaza-bicyclo [2,2,2] octane ( DABCO). The catalyst is generally used in amounts of from 1 to 50 mol% with respect to acrylic groups, preferably from 5 to 50, particularly preferably from 10 to 40 and very particularly preferably from 15 to 30 mol%.

The stoichiometry between acrylate groups and carbonyl compounds is generally 1: 0.05-1.5, preferably 1: 0.1-1.3, more preferably 1: 0.2-1.0 and most preferably 1: 0, 4 - 1.0.

The solvents used may preferably be water, petroleum ether, ligroin, toluene, benzene, xylene, tetrahydrofuran (THF), diethyl ether, dioxane or else the acrylate used. The reaction can also be carried out in the absence of a solvent.
If the acrylate is used as the solvent, the resulting reaction mixture, which contains both the acrylate used and α- (1'-hydroxyalkyl) acrylate, purified or used without separation of the acrylate as such, the acrylate then as a reactive or multifunctional Acrylate acts.

Of course, the mixture can also be purified by distillation, stripping, acidic, alkaline or neutral scrubbing, filtration or the like on a purification of the reaction mixture.

In a preferred embodiment, the carbonyl compound is used substoichiometrically in relation to the acrylate groups, so that reaction mixtures containing the Baylis-Hillman product in admixture with the acrylate used are obtained. Such mixtures can be used with advantage in coating compositions for radiation curing and / or dual-cure curing.

• mindestens eine Verbindung der Formel (V) oder der Formel (VII), und
• mindestens einen Photoinitiator (P).

Another object of the present invention are coating compositions containing

• at least one compound of the formula (V) or of the formula (VII), and
• at least one photoinitiator (P).

As photoinitiators (P) it is possible to use photoinitiators known to the person skilled in the art, for example those in " Advances in Polymer Science ", Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3 ; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London on, mentioned.

According to the invention, these mean photoinitiators that release radicals when exposed to light and can start a radical reaction, for example a free-radical polymerization.

Suitable examples are phosphine oxides, benzophenones, α-hydroxy-alkyl-aryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids and mixtures thereof.

Phosphine oxides are, for example, mono- or bisacylphosphine oxides, such as, for example, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), as described, for example, in US Pat EP-A 7 508 . EP-A 57 474 . DE-A 196 18 720 . EP-A 495 751 or EP-A 615 980 are described, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ^® TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl,
Benzophenones are, for example, benzophenone, 4-aminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,4 Dimethylbenzophenone, 4-isopropylbenzophenone, 2-chlorobenzophenone, 2,2'-dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxybenzophenone or 4-butoxybenzophenone,
Examples of α-hydroxyalkyl-aryl ketones are 1-benzoylcyclohexan-1-ol (1-hydroxycyclohexyl-phenylketone), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy-2-methyl-1-phenyl) propan-1-one), 1-hydroxyacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one or polymer containing 2-hydroxy-2- contains methyl-1- (4-isopropen-2-yl-phenyl) -propan-1-one in copolymerized form (Esacure® KIP 150)
Examples of xanthones and thioxanthones are 10-thioxanthenone, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyltrioxanthone, 2,4-dichlorothioxanthone or chloroxanthenone .
Anthraquinones are, for example, β-methylanthraquinone, tert- butylanthraquinone, anthraquinonecarbonyl acid ester, benz [de] anthracen-7-one, benz [a] anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2- tert- butylanthraquinone, 1 Chloroanthraquinone or 2-amylanthraquinone,
Acetophenones are, for example, acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, 1-acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-2-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one,
Benzoins and benzoin ethers are, for example, 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin iso-propyl ether or 7-H-benzoin methyl ether or
Ketals are, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone, or benzil ketals, such as benzil dimethyl ketal.

Phenylglyoxylic acids are for example in DE-A 198 26 712 . DE-A 199 13 353 or WO 98/33761 described.

Further usable photoinitiators are, for example, benzaldehyde, methyl ethyl ketone, 1-naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3-butanedione.

Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydroxy 2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyl.

Such coating compositions according to the invention can be used according to the invention in radiation curing.

The coating compositions according to the invention may furthermore comprise at least one reactive diluent and / or at least one multifunctional, polymerizable compound and / or further typical lacquer additives.

Reactive diluents are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 C atoms, for example (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate, vinylaromatic compounds, for example styrene, divinylbenzene, α, β-unsaturated nitriles, for example acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, eg vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, eg butadiene, Isoprene, chloroprene, monounsaturated compounds, eg ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds. for example, cyclopentene, cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid, vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as, for example: acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, Methylenmalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid, N-vinylpyrrolidone, N-vinyllactams, such as N-vinylcaprolactam, N-vinyl-N-alkyl-carboxylic acid amides or N-vinylcarboxamides, such as. B. N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, including methyl vinyl ether, ethyl vinyl ether, n -Propylvinylether, iso -Propylvinylether, n-butyl vinyl ether, sec -Butylvinylether, iso -Butylvinylether, tert Butyl vinyl ether, 4-hydroxybutyl vinyl ether, as well as mixtures thereof.

(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.

Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry at least 2, preferably 3-10, more preferably 3-6, very preferably 3-4 and in particular 3 (meth) acrylate groups, preferably acrylate groups.
These may be, for example, esters of (meth) acrylic acid with correspondingly at least dihydric polyhydric alcohols.

Such polyalcohols are, for example, at least divalent polyols, polyether or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably 3 to 10, suitable.

At least divalent polyalcohols are, for example, those as listed above in the preparation of the polyesterols.

Further suitable at least divalent polyalcohols are alkoxylated at least divalent polyalcohols of the above-mentioned formulas (IVa), (IVb) or (IVc).

Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane and / or styrene oxide.

The alkylene oxide chain may preferably be composed of ethylene oxide, propylene oxide and / or butylene oxide units. Such a chain may be composed of a species of an alkylene oxide or a mixture of alkylene oxides. When a mixture is used, the different alkylene oxide units may be random or block or blocks of individual species. Preferred is as alkylene oxide Ethylene oxide, propylene oxide or a mixture thereof, more preferably it is ethylene oxide or propylene oxide and most preferably ethylene oxide.

The number of alkylene oxide units in the chain is, for example, 1 to 20, preferably 1 to 10, particularly preferably 1 to 5 and in particular 1 to 3 and exceptionally preferably 1, based on the respective hydroxyl groups of the polyhydric alcohol.

As polyesterols are e.g. such as those already listed above.

The molecular weights M _{n of} the polyesterols or polyetherols are preferably between 100 and 4000 (M _n determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

Other multifunctional (meth) acrylates may be polyester (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates or (meth) acrylated polyacrylates, as described above as acrylates of (IVa), (IVb) or (IVc) are listed. Instead of the (meth) acrylate groups, it is also possible to use other free-radically or cationically polymerizable groups.

Urethane (meth) acrylates are e.g. obtainable by reaction of polyisocyanates with. Hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.

Preferred multifunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, (meth) acrylates of ethoxylated and / or propoxylated trimethylolpropane, pentaerythritol, glycerol or di-trimethylolpropane. Particularly preferred are acrylates of ethoxylated and / or propoxylated trimethylolpropane or pentaerythritol.

As further paint typical additives, for example, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.

As a post-curing accelerator, e.g. Tin octoate, zinc octoate, dibutyltin laureate or diaza [2.2.2] bicyclooctane.

Furthermore, one or more photochemically and / or thermally activatable initiators, such as potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis iso butyronitrile, cyclohexylsulfonyl, di- iso -propylpercarbonat, tert -Butylperoktoat or benzpinacol, and for example, such thermally activatable initiators having a half life at 80 ° C of have more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols, the z. B. commercially available under the trade name AD-DID 600 from Wacker or hydroxyl-containing amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6, 6-tetramethylpiperidine-N-oxyl etc.

Further examples of suitable initiators are described in "Polymer Handbook" 2nd ed., Wiley & Sons, New York.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.

As chelating agents, e.g. Ethylenediaminetic acid and its salts and β-diketones can be used.

Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil ^® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ^® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.

The coating compositions according to the invention can be used with advantage for dual or multi-cure applications if they additionally contain at least one compound (B) having at least one hydroxyl -OH-reactive group.

Compounds (B) having at least one hydroxy (-OH) reactive group may be, for example, isocyanates, capped isocyanates, epoxides, carbonates or aminoplasts.

Isocyanates are, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an NCO functionality of at least 1.8, preferably 1.8 to 5 and more preferably 2 to 4 in question, and their isocyanurates, biurets, urethanes, allophanates and uretdiones.

The diisocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of conventional diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate. Tetradecamethytendiisocyanat, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato 3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also aromatic Diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-DÜsocyanatodiphenylmethan and their isomer mixtures, 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, Tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

There may also be mixtures of said diisocyanates.

Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups or iminooxadiazinedione groups, uretonimine-modified polyisocyanates of straight-chain or branched C ₄ -C ₂₀ -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of from 6 to 20 ° C. -Atomen or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The usable diisocyanates and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 10 to 60% by weight, based on the diisocyanate and polyisocyanate (mixture), preferably 15 to 60% by weight and particularly preferably 20 to 55 wt%.

Preferred are aliphatic or cycloaliphatic di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Particularly preferred are hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, very particularly preferred are isophorone diisocyanate and hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate.

1. 1) Isocyanuratgruppen aufweisende Polyisocyanate von aromatischen, aliphatischen und/oder cycloaliphatischen Diisocyanaten. Besonders bevorzugt sind hierbei die entsprechenden aliphatischen und/oder cycloaliphatischen Isocyanato-Isocyanurate und insbesondere die auf Basis von Hexamethylendiisocyanat und Isophorondiisocyanat. Bei den dabei vorliegenden Isocyanuraten handelt es sich insbesondere um Tris-isocyanatoalkyl- bzw. Tris-isocyanatocycloalkyl-Isocyanurate, welche cyclische Trimere der Diisocyanate darstellen, oder um Gemische mit ihren höheren, mehr als einen Isocyanuratring aufweisenden Homologen. Die Isocyanato-Isocyanurate haben im allgemeinen einen NCO-Gehalt von 10 bis 30 Gew.%, insbesondere 15 bis 25 Gew.-% und eine mittlere NCO-Funktionalität von 2,6 bis 4,5.
2. 2) Uretdiondiisocyanate mit aromatisch, aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen, vorzugsweise aliphatisch und/oder cycloaliphatisch gebundenen und insbesondere die von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleiteten. Bei Uretdiondiisocyanaten handelt es sich um cyclische Dirnerisierungsprodukte von Diisocyanaten.
   Die Uretdiondiisocyanate können in den erfindungsgemäßen Zubereitungen als alleinige Komponente oder im Gemisch mit anderen Polyisocyanaten, insbesondere den unter 1) genannten, eingesetzt werden.
3. 3) Biuretgruppen aufweisende Polyisocyanate mit aromatisch, cycloaliphatisch oder aliphatisch gebundenen, bevorzugt cycloaliphatisch oder aliphatisch gebundenen Isocyanatgruppen, insbesondere Tris(6-isocyanatohexyl)biuret oder dessen Gemische mit seinen höheren Homologen. Diese Biuretgruppen aufweisenden Polyisocyanate weisen im allgemeinen einen NCO-Gehalt von 18 bis 22 Gew.-% und eine mittlere NCO-Funktionalität von 2,8 bis 4,5 auf.
4. 4) Urethan- und/oder Allophanatgruppen aufweisende Polyisocyanate mit aromatisch, aliphatisch oder cycloaliphatisch gebundenen, bevorzugt aliphatisch oder cycloaliphatisch gebundenen Isocyanatgruppen, wie sie beispielsweise durch Umsetzung von überschüssigen Mengen an Hexamethylendiisocyanat oder an Isophorondiisocyanat mit ein- oder mehrwertigen Alkoholen wie z.B. Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, iso-Butanol, sek-Butanol, tert-Butanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, n-Dodecanol (Laurylalkohol), 2-Ethylhexanol, n-Pentanol, Stearylalkohol, Cetylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, 1,3-Propandiolmonomethylether, Cyclopentanol, Cyclohexanol, Cyclooctanol, Cyclododecanol oder mehrwertige Alkohole, wie sie oben bei den Polyesterolen aufgeführt sind, oder deren Gemischen erhalten werden können. Diese Urethan- und/oder Allophanatgruppen aufweisenden Polyisocyanate haben im allgemeinen einen NCO-Gehalt von 12 bis 20 Gew.-% und eine mittlere NCO-Funktionalität von 2,5 bis 4,5.
5. 5) Oxadiazintriongruppen enthaltende Polyisocyanate, vorzugsweise von Hexamethylendüsocyanat oder Isophorondiisocyanat abgeleitet. Solche Oxadiazintriongruppen enthaltenden Polyisocyanate sind aus Diisocyanat und Kohlendioxid herstellbar.
6. 6) Iminooxadiazindiongruppen enthaltende Polyisocyanate, vorzugsweise von Hexamethylendüsocyanat oder Isophorondiisocyanat abgeleitet. Solche Iminooxadiazindiongrupperi enthaltenden Polyisocyanate sind aus Diisocyanaten mittels spezieller Katalysatoren herstellbar.
7. 7) Uretonimin-modifizierte Polyisocyanate.

Further preferred

1. 1) isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt.%, In particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 4.5.
2. 2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dirnerization products of diisocyanates.
   The uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
3. 3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 4.5.
4. 4) polyisocyanates containing urethane and / or allophanate groups with aromatic, aliphatic or cycloaliphatic bound, preferably aliphatically or cycloaliphatically bound isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with monohydric or polyhydric alcohols, for example methanol, ethanol, Iso -propanol, n-propanol, n-butanol, iso -butanol, sec- butanol, tert- butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol , n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol or polyhydric alcohols, as listed above for the polyesterols, or mixtures thereof. These urethane and / or allophanate polyisocyanates generally have a NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.
5. 5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.
6. 6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such iminooxadiazinedione group-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
7. 7) Uretonimine-modified polyisocyanates.

The polyisocyanates 1) to 7) can be used in a mixture, if appropriate also in a mixture with diisocyanates.

The isocyanate groups may also be present in capped form. Suitable capping agents for NCO groups are, for example, oximes, phenols, imidazoles, pyrazoles, pyrazolinones, diketopiperazines, caprolactam, malonic acid esters or compounds as mentioned in the publications of ZW Wicks, Prog. Org. Coat. 3 (1975) 73-99 and Prog. Org. Coat 9 (1981), 3-28 as in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 2, 61 ff. Georg Thieme Verlag, Stuttgart 1963 ,

By blocking or blocking agents are meant compounds which convert isocyanate groups into blocked (capped or protected) isocyanate groups, which then do not exhibit the usual reactions of a free isocyanate group below the so-called deblocking temperature. Such compounds having blocked isocyanate groups are commonly used in dual-cure coatings that are finally cured via isocyanate group cure.

Epoxy compounds are those having at least one, preferably having at least two, preferably two or three epoxide groups in the molecule.

Suitable examples include epoxidized olefins, glycidyl esters (eg glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or aromatic polyols. Such products are commercially available in large numbers. Particularly preferred are polyglycidyl compounds of the bisphenol A, F or B type and glycidyl ethers of polyfunctional alcohols, for example butanediol, 1,6-hexanediol, glycerol and pentaerythritol. Examples of such polyepoxide compounds are Epikote ^® 812 (epoxide value: about 0.67 mol / 100g) and Epikote ^® 828 (epoxide value: about 0.53 mol / 100g), Epikote ^® 1001, Epikote ^® 1007, and Epikote ^® 162 (epoxide value: about 0.61 mol / 100 g) from Resolution, Rutapox® 0162 (epoxide value: about 0.58 mol / 100g), Rütapox ^® 0164 (epoxide value: about 0.53 mol / 100g) and Rütapox ^® 0165 (epoxide value: about 0.48 mol / 100g) Bakelite AG, Araldite ^® DY 0397 (epoxide value: approx 0, 83 mol / 100 g) of the company Vantico AG.

Carbonate compounds are those having at least one, preferably having at least two, preferably two or three carbonate groups in the molecule, which preferably contain terminal C ₁ -C ₂₀ alkylcarbonate groups, more preferably terminal C ₁ -C ₄ alkyl carbonate groups, very particularly preferably terminal methyl carbonate, ethyl carbonate or n-butyl carbonate.

Other suitable components (B) are compounds having active methylol or alkylalkoxy groups, in particular methylalkoxy groups, on aminoplast crosslinking agents, for example etherified reaction products of formaldehyde with amines, such as melamine, urea, etc., phenol / formaldehyde adducts, siloxane or silane groups and anhydrides , as in eg US 5,770,650 are described.

Among the technically widespread and known, preferred aminoplasts are particularly preferred urea resins and melamine resins, such. Urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-urea-formaldehyde resins, usable.

Suitable urea resins are those which are obtainable by reacting ureas with aldehydes and can be modified if appropriate.

As ureas, urea, N-substituted or N, N'-disubstituted ureas are suitable, e.g. N-methylurea, N-phenylurea, N, N'-dimethylurea, hexamethylenediurea, N, N'-diphenylurea, 1,2-ethylenediurea, 1,3-propylenediurea, diethylenetriurea, dipropylenetriurea, 2-hydroxypropylenediurea, 2-imidazolidinone ( Ethyleneurea), 2-oxohexahydropyrimidine (propyleneurea) or 2-oxo-5-hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).

Urea resins may optionally be partially or fully modified, e.g. by reaction with mono- od. polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionic modified urea resins), particularly suitable are the alcohol-modified urea resins.

Suitable alcohols for the modification C ₁ - C ₆ -alcohols in question, preferably C ₁ - C ₄ -alcohol and in particular methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol and sec- butanol.

Suitable melamine resins are those which are obtainable by reacting melamine with aldehydes and which may optionally be partially or completely modified.

As aldehydes especially formaldehyde, acetaldehyde, iso butyraldehyde and glyoxal are suitable.

Melamine-formaldehyde resins are reaction products of the reaction of melamine with aldehydes, e.g. the o.g. Aldehydes, especially formaldehyde. Optionally, the resulting methylol groups are modified by etherification with the above-mentioned monohydric or polyhydric alcohols. Furthermore, the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites.

By the action of formaldehyde on mixtures of melamine and urea or on mixtures of melamine and phenol, melamine-urea-fonilaldehyde resins or melamine-phenol-formaldehyde resins which can also be used according to the invention are also produced according to the invention.

The production of said aminoplasts is carried out according to known methods.

Particular examples are melamine-formaldehyde resins, including monomeric or polymeric melamine resins and partially or fully alkylated melamine resins, urea resins, for example methylol ureas such as formaldehyde-urea resins, alkoxy ureas such as butylated formaldehyde-urea resins, but also N-methylolacrylamide emulsions, iso- butoxy-methyl acrylamide emulsions, polyanhydrides, such as, for example, polysuccinic anhydride, and siloxanes or silanes, for example dimethyldimethoxysilanes.

Particularly preferred are aminoplast resins such as melamine-formaldehyde resins or formaldehyde urea resins.

Also disclosed is a process for coating substrates in which a coating composition according to the invention is used.

The substrates are coated by customary methods known to the person skilled in the art, at least one coating composition or lacquer formulation according to the invention being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating composition removed, if appropriate with heating. If desired, this process can be repeated one or more times. The application to the substrate can be carried out in a known manner, z. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

Furthermore, a process for coating substrates is disclosed, in which the coating compositions of the invention or coating formulations containing them, optionally mixed with further typical coatings additives and thermally curable resins, applied to the substrate and optionally dried, with electron beams or UV exposure under an oxygen-containing atmosphere or preferred cured under inert gas, optionally at temperatures up to the height of the drying temperature and then at temperatures up to 160 ° C, preferably between 60 and 160 ° C, thermally treated.

The process for coating substrates can also be carried out so that after application of the coating composition of the invention or paint formulations initially at temperatures up to 160 ° C, preferably between 60 and 160 ° C, thermally treated and then with electron beams or UV exposure under oxygen or is preferably cured under inert gas.

If desired, the curing of the films formed on the substrate can be effected exclusively thermally. Generally and preferably, however, the coatings are cured by both high energy irradiation and thermal.

Optionally, if a plurality of layers of the coating composition are applied to one another, thermal and / or radiation curing can take place after each coating operation.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse emitters, metal halide lamps, electronic flash devices, whereby a radiation curing without photoinitiator is possible, or Excimerstrahler. The radiation is cured by exposure to high-energy radiation, ie UV radiation or daylight, preferably light in the wavelength range of λ = 200 to 700 nm, particularly preferably from λ = 200 to 500 nm and most preferably λ = 250 to 400 nm, or by Irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

Of course, several radiation sources for curing can be used, for example, two to four.

These can also radiate in different wavelength ranges.

The curing can also be carried out in addition to or instead of the thermal curing by NIR radiation, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.

1. i) ein Substrat mit einer Beschichtungsmasse, wie zuvor beschrieben, beschichtet,
2. ii) flüchtige Bestandteile der Beschichtungsmasse zur Filmbildung unter Bedingungen entfernt, bei denen der Initiator (P) im wesentlichen noch keine freien Radikale ausbildet,
3. iii) gegebenenfalls den in Schritt ii) gebildeten Film mit energiereicher Strahlung bestrahlt, wobei der Film vorgehärtet wird, und anschließend gegebenenfalls den mit dem vorgehärteten Film beschichteten Gegenstand mechanisch bearbeitet oder die Oberfläche des vorgehärteten Films mit einem anderen Substrat in Kontakt bringt,
4. iv) dem Film thermisch endhärtet.

If appropriate, the irradiation can also be carried out with the exclusion of oxygen, for example under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Furthermore, the irradiation can be carried out by covering the coating composition with transparent media. Transparent media are z. As plastic films, glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner as described in US Pat DE-A1 199 57 900 is described.
Another object of the invention is a method for coating substrates, wherein

1. i) coating a substrate with a coating composition as described above,
2. ii) removing volatile constituents of the coating composition for film formation under conditions in which the initiator (P) still substantially does not form free radicals,
3. iii) optionally irradiating the film formed in step ii) with high energy radiation, whereby the film is precured, then optionally mechanically working the precured film coated article or contacting the surface of the precured film with another substrate,
4. iv) thermally cures the film.

In this case, the steps iv) and iii) can also be performed in reverse order, d. H. The film can first be cured thermally and then with high energy radiation.

The coating compositions and coating formulations according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement boards, or metals or coated metals, preferably of plastics or metals , which may be present as films, for example.

The coating compositions according to the invention are particularly preferably suitable as or in exterior coatings, ie those applications which are exposed to daylight, preferably of buildings or building parts, interior coatings, road markings, Coatings on vehicles and aircraft. In particular, the coating compositions of the invention are used as or in automotive clearcoat and topcoat (s).

Another object of the invention is the use of α- (1'-hydroxyalkyl) acrylates in coating compositions for dual-cure applications.

Another object of the invention is the use of compounds of formula (V) or (VII) in radiation curing.

The following examples are intended to illustrate the characteristics of the invention without, however, limiting it.

Examples

As "parts" or "%" in this document, unless otherwise stated, "parts by weight" or "weight%" understood.

The Erichsentiefung was determined according to DIN 53156 and is a measure of flexibility and elasticity. The information is given in millimeters (mm). High values mean high flexibility. Unless otherwise indicated, the Erichsen relief films were applied to sheet metal using spiral irons. The layer thickness after the exposure was 40 μm unless otherwise specified.

The pendulum hardness was determined according to DIN 53157 and is a measure of the hardness of the coating. The information is given in seconds (s). High values mean high hardness. The Pendulum Hardness films were applied to glass using a doctor blade unless otherwise specified. The layer thickness after exposure was 70 μm unless otherwise specified.

The OH number was gem. DIN 53240 determined.

Example 1:

148 parts of trimethylolpropane triacrylate, 17 parts of diaza-bicyclo-octane, 100 parts of tetrahydrofuran and 150 parts of formaldehyde solution (36%) were combined in a reaction flask and stirred at 60 ° C for 2 hours.
Then, 100 parts of diethyl ether were added, shaken 2 times with 100 parts of 1 N hydrochloric acid and 1 time with aqueous sodium chloride solution, the phases were separated, the organic phase was dried over sodium sulfate, 1 part of phenothiazine was added and the solvent was distilled off.

The result was a clear, slightly yellowish liquid which had a marked OH band at 3500 cm-1 in the IR spectrum (OH number 109 mgKOH / g) and a shift of the unsubstituted acrylate band at 810 cm ^-1 after 820 cm ^-1 . No free trimethylolpropane triacrylate was present in the GC chromatogram.

Example 2:

148 parts of trimethylolpropane triacrylate, 5.6 parts of diaza-bicyclo-octane, 100 parts of tetrahydrofuran and 50 parts of formaldehyde solution (36%) were combined in a reaction flask and stirred at 60 ° C for 2 hours.
Then, 100 parts of diethyl ether were added, shaken 2 times with 100 parts of 1 N hydrochloric acid and 1 time with aqueous sodium chloride solution, the phases were separated, the organic phase was dried over sodium sulfate, 1 part of phenothiazine was added and the solvent was distilled off.

The result was a clear liquid with a viscosity of 510 mPas, which had a significant OH band at 3500 cm ^-1 in the IR spectrum (OH number 63 mgKOH / g). The GC chromatogram still contained 23 area percent free trimethylolpropane triacrylate.

Example 3:

302 parts triacrylate of seven times ethoxylated trimethylolpropane, 17 parts of diaza-bicyclo-octane, 100 parts of tetrahydrofuran and 150 parts of formaldehyde solution (36%) were combined in a reaction flask and stirred at 60 ° C for 2 hours.

Then, 100 parts of diethyl ether were added, shaken 2 times with 100 parts of 1 N hydrochloric acid and 1 time with aqueous sodium chloride solution, the phases were separated, the organic phase was dried over sodium sulfate, 1 part of phenothiazine was added and the solvent was distilled off.

The result was a clear, slightly yellowish liquid, which had a significant OH band at 3500 cm ^-1 in the IR spectrum.

Example 4:

500 parts of a polyester acrylate commercially available (Laromer ^® PE 55F, BASF Aktiengesellschaft), 14 parts diaza-bicyclo-octane 100 parts of tetrahydrofuran and 125 Parts of formaldehyde solution (36%) are combined in a reaction flask and stirred at 60 ° C for 2 hours.
100 parts of diethyl ether are then added, the mixture is shaken twice with 100 parts of 1 N hydrochloric acid and once with aqueous sodium chloride solution, the phases are separated, the organic phase is dried over sodium sulfate, 1 part of phenothiazine is added and the solvent is distilled off.
The result is a clear, slightly yellowish liquid, which has a significant OH band at 3500 cm ^-1 in the IR spectrum.

Example 5:

215 parts of an epoxy acrylate commercially available ((Laromer ^® EA 81, BASF Aktiengesellschaft), 11 parts of diaza-bicyclo-ocfan, 100 parts of tetrahydrofuran and 100 parts of formaldehyde solution (36% strength) are combined in a reaction flask and stirred for 2 hours at 60 ° C ,

Then, 100 parts of diethyl ether, shaken 2 times with 100 parts of 1 N hydrochloric acid and 1 times with aqueous sodium chloride solution, the phases are separated, the organic phase is dried over sodium sulfate, 1 part of phenothiazine is added and the solvent is distilled off.

The result is a clear, slightly yellowish liquid, which has a significantly increased OH band at 3500 cm ^-1 in the IR spectrum compared to the starting compound.

Example 6:

750 parts of a urethane acrylate commercially available ((Laromer ^® UA19T, BASF Aktiengesellschaft), 11 parts of diaza-bicyclo-octane 100 parts of tetrahydrofuran and 100 parts of formaldehyde solution (36% strength) are combined in a reaction flask and stirred at 60 ° C for 2 hours.

100 parts of diethyl ether are then added, the mixture is shaken twice with 100 parts of 1 N hydrochloric acid and once with aqueous sodium chloride solution, the phases are separated, the organic phase is dried over sodium sulfate, 1 part of phenothiazine is added and the solvent is distilled off.

The result is a clear, pale yellowish liquid, which has a significant OH band at 3500 cm ^-1 in the IR spectrum in addition to the NH band.

Example 7: Dual Cure Application

10 parts of the α-hydroxyalkyl acrylate prepared according to Example 1 were mixed with 3.8 parts of a trimeric isocyanurate of hexamethylene diisocyanate and applied in a layer thickness of about 5 microns to a KBr IR platelets. The IR spectrum showed the OH bands at 3500 cm ^-1 , the NCO bands at 2250 cm ^-1 and the acrylate bands at 820 cm ^-1 . Upon annealing the IR crystal at 180 ° C for 2 hours, the NCO band disappeared almost completely at 2250 cm ^-1 , the acrylate band reduced and the OH band shifted to 3350 cm ^-1 (NH). By subsequent exposure, the acrylate band also disappeared almost completely. Similar results were obtained when first exposed and then heated at 180 ° C.

Example 8:

10 parts of the α-hydroxyalkyl acrylate prepared according to Example 1 were (Ciba Specialties) was added with 0.4 parts of the photoinitiator Darocure ^® 1173, and applied in a layer thickness of about 50 micrometers on a glass plate and exposed to light at 1200 mJ / cm ^2. This resulted in a pendulum hardness of 140 s and an Erichsen recess of 0.5 mm.

Comparative Example 1

Trimethylolpropane triacrylate was processed in place of the reaction product of Example 1 under the same conditions as in Example 8. This resulted in a pendulum hardness of 172 s and a Erichsen relief of 0.

Example 8 and Comparative Example 1 show that with the alpha-hydroxyacrylates according to the invention similar properties are obtained after UV exposure in terms of hardness and flexibility as with unsubstituted acrylate and Example 7 shows that it is possible to produce dual care lacquers according to the invention.

Claims (10)

1. A compound of the formula (V),

   

   in which
   R² and R³ independently of one another are C₁-C₁₈ alkyl, C₂-C₁₈ alkyl if appropriate interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C₂-C₁₈ alkenyl, C₆-C₁₂ aryl, C₅-C₁₂ cycloalkyl or a five- to six-membered oxygen-, nitrogen- and/or sulfur-containing heterocycle, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,
   R² and/or R³ are/is additionally hydrogen, C₁-C₁₈ alkoxy optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, or -COOR⁴,
   R² may additionally together with R¹ form a ring, in which case R² can be a carbonyl group, so that the group COOR¹ and R² together form an acid anhydride group -(CO)-O-(CO)-,
   R⁴ is C₁-C₁₈ alkyl, C₂-C₁₈ alkyl if appropriate interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C₂-C₁₈ alkenyl, C₆-C₁₂ aryl, C₅-C₁₂ cycloalkyl or a five- to six-membered oxygen-, nitrogen- and/or sulfur-containing heterocycle, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,
   R⁵ and R⁶ independently of one another are hydrogen, C₁-C₁₈ alkyl, C₂-C₁₈ alkyl if appropriate interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C₂-C₁₈ alkenyl, C₆-C₁₂ aryl, C₅-C₁₂ cycloalkyl or a five- to six-membered oxygen-, nitrogen- and/or sulfur-containing heterocycle, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, or may together form a ring,
   n is a positive integer from 3 to 10, and
   R⁷ is an n-valent organic radical having 1 to 50 carbon atoms which can be unsubstituted or substituted by halogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, carboxyl, carboxy-C₁-C₈ alkyl, C₁-C₂₀ acyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, hydroxyl or hydroxy-substituted C₁-C₈ alkyl and/or can contain one or more -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O- groups.
2. The compound according to claim 1, wherein n is 3 or 4 and
   R⁷ is derived from an n-hydric alcohol by removing n hydroxyl groups,
   the n-hydric alcohol being trimethylolpropane, pentaerythritol or a singly to vigintuply ethoxylated trimethylolpropane.
3. A coating composition comprising

   - at least one compound of the formula (V) as defined in claim 1, or of the formula (VII) as defined in claim 10, and

   - at least one photoinitiator (P).
4. The coating composition according to claim 3, further comprising

   - at least one reactive diluent and/or

   - at least one polyfunctional polymerizable compound.
5. The coating composition according to claim 3 or 4, further comprising

   - at least one compound (B) containing at least one hydroxy (-OH)-reactive group.
6. A method of coating substrates, wherein a coating composition according to any one of claims 3 to 5 is used.
7. A substrate coated with a coating composition according to any one of claims 3 to 5.
8. A process for preparing a compound of the formula (V)

   

   as defined in claim 1, it being possible for n to be additionally 2, wherein the compound (II) is an aldehyde R⁵-CHO and is used in free form so that in formals of the formula (R⁵-CHO)_w, in which w is a positive integer, w is ≤ 20.
9. The use of α-(1'-hydroxyalkyl)acrylates in coating compositions for dual-cure applications.
10. The use of compounds of the formula (V) as defined in claim 8 or (VII)

    

    in which R² and R³ are as defined in claim 1,
    R¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkyl if appropriate interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C₂-C₁₈ alkenyl, C₆-C₁₂ aryl, C₅-C₁₂ cycloalkyl or a five- to six-membered oxygen-, nitrogen- and/or sulfur-containing heterocycle, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, and
    R⁸ is unsubstituted or halogen-, C₁-C₈ alkyl-, C₂-C₈ alkenyl-, carboxyl-, carboxy-C₁-C₈ alkyl-, C₁-C₂₀ acyl-, C₁-C₈ alkoxy-, C₆-C₁₂ aryl-, hydroxyl- or hydroxy-substituted C₁-C₈ alkyl-substituted C₆-C₁₂ arylene, C₃-C₁₂ cycloalkylene or C₁-C₂₀ alkylene or is C₂-C₂₀ alkylene interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups and/or by one or more -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O-groups or is a single bond
    in radiation curing.